JP2006249416A - Curable perfluoropolyether composition, rubber and gel product using the cured product - Google Patents
Curable perfluoropolyether composition, rubber and gel product using the cured product Download PDFInfo
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- JP2006249416A JP2006249416A JP2006029683A JP2006029683A JP2006249416A JP 2006249416 A JP2006249416 A JP 2006249416A JP 2006029683 A JP2006029683 A JP 2006029683A JP 2006029683 A JP2006029683 A JP 2006029683A JP 2006249416 A JP2006249416 A JP 2006249416A
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- Prior art keywords
- perfluoropolyether
- group
- component
- compound
- rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 89
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 239000005060 rubber Substances 0.000 title claims abstract description 53
- 239000000499 gel Substances 0.000 title 1
- 239000007789 gas Substances 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 11
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- -1 Dimethylphenylsilylene group Chemical group 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
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- 230000001681 protective effect Effects 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 7
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- 238000004382 potting Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 150000003058 platinum compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 229940045985 antineoplastic platinum compound Drugs 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HMVBQEAJQVQOTI-SOFGYWHQSA-N (e)-3,5-dimethylhex-3-en-1-yne Chemical compound CC(C)\C=C(/C)C#C HMVBQEAJQVQOTI-SOFGYWHQSA-N 0.000 description 1
- GRGVQLWQXHFRHO-AATRIKPKSA-N (e)-3-methylpent-3-en-1-yne Chemical compound C\C=C(/C)C#C GRGVQLWQXHFRHO-AATRIKPKSA-N 0.000 description 1
- VHVMXWZXFBOANQ-UHFFFAOYSA-N 1-Penten-3-ol Chemical compound CCC(O)C=C VHVMXWZXFBOANQ-UHFFFAOYSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- MQSZOZMNAJHVML-UHFFFAOYSA-N 3-phenylbut-1-yn-1-ol Chemical compound OC#CC(C)C1=CC=CC=C1 MQSZOZMNAJHVML-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005040 ion trap Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Measuring Fluid Pressure (AREA)
- Polyethers (AREA)
Abstract
Description
本発明は、耐熱性、耐油性、耐薬品性、耐溶剤性、低温特性、耐湿性、低気体透過性等に優れ、特には酸性ガス低透過性硬化物を形成する、硬化してゴムを形成することを特徴とする硬化性パーフルオロポリエーテル組成物（以下、パーフルオロポリエーテルゴム組成物という）及び硬化してゲルを形成することを特徴とする硬化性パーフルオロポリエーテル組成物（以下、パーフルオロポリエーテルゲル組成物という）、並びにその硬化物を用いたゴム及びゲル製品に関する。 The present invention is excellent in heat resistance, oil resistance, chemical resistance, solvent resistance, low temperature characteristics, moisture resistance, low gas permeability, etc., and in particular, forms an acid gas low permeability cured product. A curable perfluoropolyether composition (hereinafter referred to as a perfluoropolyether rubber composition) characterized by forming and a curable perfluoropolyether composition (hereinafter referred to as a perfluoropolyether rubber composition) which is cured to form a gel , Perfluoropolyether gel composition), and rubber and gel products using the cured product thereof.
従来、１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する直鎖状パーフルオロポリエーテル化合物、１分子中にＨ−ＳｉＯＳｉＯ構造を２個以上有する有機ケイ素化合物及びヒドロシリル化反応触媒からなる組成物から、耐熱性、耐薬品性、耐溶剤性、撥水性、撥油性、耐候性等の性質がバランスよく優れた硬化物を得ることができることが提案されている（特許文献１：特許第２９９０６４６号公報、特許文献２：特開２０００−２４８１６６号公報参照）。 Conventionally, a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, and having two or more H-SiOSiO structures in one molecule It is proposed that a cured product having a well-balanced property such as heat resistance, chemical resistance, solvent resistance, water repellency, oil repellency, and weather resistance can be obtained from a composition comprising an organosilicon compound and a hydrosilylation reaction catalyst. (See Patent Document 1: Japanese Patent No. 2990646, Patent Document 2: Japanese Patent Laid-Open No. 2000-248166).
しかしながら、このようなパーフルオロポリエーテルゴム組成物は、殆どの用途においてはこれで十分な性能を有しているものの、耐薬品性を要求される半導体製造装置用シール剤等の材料、エンジンオイル用に使用されるシール剤及びポッティング剤、エンジンの排気系部品に使用されるシール剤及びポッティング剤等の用途では、ゴムあるいはゲル製品は電気電子部品の腐食を防止、遅延することが強く望まれていた。特に、気体としての酸性ガス及び硫黄含有ガスによる腐食を防止、遅延することが必要とされる場合がある。それ故、耐油性、耐薬品性、特に酸性ガス及び硫黄含有ガスの低透過性に優れるパーフルオロポリエーテルゴム又はパーフルオロポリエーテルゲル組成物の出現が強く望まれていた。 However, although such a perfluoropolyether rubber composition has sufficient performance in most applications, it is a material such as a sealant for semiconductor manufacturing equipment that requires chemical resistance, engine oil, etc. In applications such as sealants and potting agents used in automobiles, and sealants and potting agents used in engine exhaust system parts, it is strongly desired that rubber or gel products prevent and delay corrosion of electrical and electronic parts. It was. In particular, it may be necessary to prevent and delay corrosion due to acidic gases and sulfur-containing gases as gases. Therefore, there has been a strong demand for the appearance of perfluoropolyether rubber or perfluoropolyether gel composition that is excellent in oil resistance, chemical resistance, particularly low permeability of acid gas and sulfur-containing gas.
本発明は、上記事情に鑑みなされたもので、耐熱性、耐薬品性、耐溶剤性、撥水性、撥油性、耐候性、離型性等に優れている上、特に酸性ガス及び硫黄含有ガスの低透過性に優れた硬化物を与える硬化性パーフルオロポリエーテルゴム組成物又は硬化性パーフルオロポリエーテルゲル組成物及びそれらの硬化物を含むゴム及びゲル製品を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is excellent in heat resistance, chemical resistance, solvent resistance, water repellency, oil repellency, weather resistance, releasability and the like, and in particular, acidic gas and sulfur-containing gas. An object of the present invention is to provide a curable perfluoropolyether rubber composition or a curable perfluoropolyether gel composition that gives a cured product excellent in low permeability of the rubber, and a rubber and gel product containing the cured product.
本発明者らは、上記目的を達成するため鋭意検討を行った結果、パーフルオロポリエーテルゴム組成物又はパーフルオロポリエーテルゲル組成物に対し、酸素ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体を配合することにより、硬化物の体積抵抗率が１×１０9Ω・ｃｍ以上の非導電性ゴム又はゲルを形成すると共に、このゴム又はゲル中において、この粉体が酸性ガス及び／又は硫黄含有ガスと反応もしくは吸着することにより電気電子部品の腐食を防止、遅延することを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention chemically and / or oxygen gas and / or sulfur-containing gas to the perfluoropolyether rubber composition or perfluoropolyether gel composition. Or, by blending inorganic powder that can be physically adsorbed, the volume resistivity of the cured product forms a non-conductive rubber or gel with a resistance of 1 × 10 9 Ω · cm or more, and in this rubber or gel, It has been found that this powder prevents or delays corrosion of electric and electronic parts by reacting or adsorbing with acid gas and / or sulfur-containing gas, and has led to the present invention.
従って、本発明は、
（Ａ）１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に−ＣaＦ2aＯ−の繰り返し単位を含むパーフルオロポリエーテル構造を有する、直鎖状パーフルオロポリエーテル化合物（ａは１〜６の整数） １００質量部
（Ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物 硬化有効量
（Ｃ）酸性ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体
０．１〜５０質量部
（Ｄ）ヒドロシリル化反応触媒 触媒量
を含有し、硬化してゴムを形成することを特徴とする硬化性パーフルオロポリエーテル組成物を提供する。
また、本発明は、
（Ａ）１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中に−ＣaＦ2aＯ−の繰り返し単位を含むパーフルオロポリエーテル構造を有する、直鎖状パーフルオロポリエーテル化合物（ａは１〜６の整数） ２５〜６５質量部
（Ｅ）１分子中に１個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する、ポリフルオロモノアルケニル化合物 ７５〜３５質量部
（但し、（Ａ），（Ｅ）成分の合計量を１００質量部とする）
（Ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物 硬化有効量
（Ｃ）酸性ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体
０．１〜５０質量部
（Ｄ）ヒドロシリル化反応触媒 触媒量
を含有し、硬化してゲルを形成することを特徴とする硬化性パーフルオロポリエーテル組成物を提供する。この場合、（Ｅ）成分が、下記一般式（２）
Ｒｆ1−（Ｘ’）p−ＣＨ＝ＣＨ2 （２）
［式中、Ｘ’及びｐは下記の通りであり、Ｒｆ1は、下記一般式
Ｆ−［ＣＦ（ＣＦ3）ＣＦ2Ｏ］w−ＣＦ（ＣＦ3）−
（式中、ｗは１〜５００の整数で表される。）で示されるパーフルオロポリエーテル構造である。］
で表されるポリフルオロモノアルケニル化合物であることが好ましい。
また、（Ａ）成分が下記一般式（１）
で表される直鎖状パーフルオロポリエーテル化合物であることが好ましい。
一方、（Ｃ）成分としては、銅等の金属粉、細孔構造を有する粉体活性炭、ハイドロタルサイト構造を有する粉体化合物の１種又は２種以上が好ましい。
また、前記パーフルオロポリエーテル組成物が、更に（Ｆ）成分として、下記一般式（３）
Ａ−Ｏ−（ＣＦ2ＣＦ2ＣＦ2Ｏ）d−Ａ （３）
［式中、Ａは式：ＣeＦ2e+1−（ｅは１〜３）で表される基であり、ｄは１〜５００の整数。］、及び、下記一般式（４）
Ａ−Ｏ−（ＣＦ2Ｏ）f（ＣＦ2ＣＦ2Ｏ）h−Ａ （４）
（式中、Ａは上記と同じであり、ｆ及びｈはそれぞれ１〜３００の整数。）
で表される化合物からなる群から選ばれる少なくとも１種の直鎖状ポリフルオロ化合物を含有することができる。
上記パーフルオロポリエーテル組成物の硬化物の体積抵抗率は１×１０9Ω・ｃｍ以上の非導電性ゴム又はゲルであることが好ましいが、本発明は上記パーフルオロポリエーテル組成物の硬化物を含むゴム又はゲル製品、特に自動車用、化学プラント用、インクジェットプリンタ用、半導体製造ライン用、分析・理化学機器用、医療機器用、航空機用又は燃料電池用材料であるゴム又はゲル製品を提供する。
更に、本発明は、圧力を検出してその検出値に応じたレベルの電気信号を発生する検出部を、耐薬品性を有する保護部材で被覆して保護するようにした圧力センサーにおいて、保護部材として、上記の硬化性パーフルオロポリエーテル組成物を用いることを特徴とする自動車用圧力センサーを提供する。
Therefore, the present invention
(A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure containing a repeating unit of -C a F 2a O- in the main chain (A is an integer of 1 to 6) 100 parts by mass (B) Organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule Curing effective amount (C) Acid gas and / or sulfur-containing gas Inorganic powder that can be adsorbed physically and / or physically
0.1 to 50 parts by mass (D) Hydrosilylation reaction catalyst Provided is a curable perfluoropolyether composition containing a catalytic amount and cured to form a rubber.
The present invention also provides:
(A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure containing a repeating unit of -C a F 2a O- in the main chain (A is an integer of 1 to 6) 25 to 65 parts by mass (E) Polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain 75 to 35 parts by mass
(However, the total amount of components (A) and (E) is 100 parts by mass)
(B) Organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule Curing effective amount (C) Inorganic powder capable of chemically and / or physically adsorbing acid gas and / or sulfur-containing gas body
0.1 to 50 parts by mass (D) Hydrosilylation reaction catalyst Provided is a curable perfluoropolyether composition containing a catalytic amount and cured to form a gel. In this case, the component (E) is represented by the following general formula (2)
Rf 1 − (X ′) p —CH═CH 2 (2)
[Wherein, X ′ and p are as follows, and Rf 1 represents the following general formula: F- [CF (CF 3 ) CF 2 O] w —CF (CF 3 ) —
(Wherein w is represented by an integer of 1 to 500). ]
It is preferable that it is a polyfluoromonoalkenyl compound represented by these.
In addition, the component (A) is represented by the following general formula (1)
It is preferable that it is the linear perfluoro polyether compound represented by these.
On the other hand, the component (C) is preferably one or more of metal powders such as copper, powdered activated carbon having a pore structure, and powder compounds having a hydrotalcite structure.
Further, the perfluoropolyether composition may further contain the following general formula (3) as component (F):
A-O- (CF 2 CF 2 CF 2 O) d -A (3)
[Wherein, A is a group represented by the formula: C e F 2e + 1- (e is 1 to 3), and d is an integer of 1 to 500. And the following general formula (4)
A-O- (CF 2 O) f (
(In the formula, A is the same as above, and f and h are each an integer of 1 to 300.)
And at least one linear polyfluoro compound selected from the group consisting of compounds represented by
The volume resistivity of the cured product of the perfluoropolyether composition is preferably a non-conductive rubber or gel of 1 × 10 9 Ω · cm or more, but the present invention is a cured product of the perfluoropolyether composition. In particular, rubber or gel products that are materials for automobiles, chemical plants, inkjet printers, semiconductor production lines, analytical / physical equipment, medical equipment, aircraft, or fuel cells are provided. .
Furthermore, the present invention relates to a pressure sensor that protects a detection unit that detects a pressure and generates an electric signal of a level corresponding to the detected value with a protective member having chemical resistance. As an automotive pressure sensor, the curable perfluoropolyether composition is used.
本発明のパーフルオロポリエーテル組成物は、耐熱性、耐油性、耐薬品性、耐溶剤性、低温特性、耐湿性、低気体透過性等に優れ、特には酸性ガス及び硫黄含有ガスの低透過性に優れた硬化物を与える。 The perfluoropolyether composition of the present invention is excellent in heat resistance, oil resistance, chemical resistance, solvent resistance, low temperature characteristics, moisture resistance, low gas permeability, etc., especially low permeation of acid gas and sulfur-containing gas. Gives a cured product with excellent properties.
本発明の（Ａ）成分は、１分子中に少なくとも２個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造、好ましくは二価のパーフルオロアルキルエーテル構造を有するものである。 The component (A) of the present invention has at least two alkenyl groups in one molecule and a perfluoropolyether structure, preferably a divalent perfluoroalkyl ether structure in the main chain.
ここで、パーフルオロアルキルエーテル構造としては、−ＣaＦ2aＯ−（式中、各単位のａは独立に１〜６の整数である。）の多数の繰り返し単位を含むもので、例えば下記一般式（５）で示されるものなどが挙げられる。
（ＣaＦ2aＯ）q （５）
（式中、ｑは５０〜６００、好ましくは５０〜４００、より好ましくは５０〜２００の整数である。）
Here, the perfluoroalkyl ether structure includes a large number of repeating units of —C a F 2a O— (wherein a in each unit is an integer of 1 to 6). Examples thereof include those represented by the general formula (5).
(C a F 2a O) q (5)
(In the formula, q is an integer of 50 to 600, preferably 50 to 400, more preferably 50 to 200.)
上記式（５）で示される繰り返し単位−ＣaＦ2aＯ−としては、例えば下記の単位等が挙げられる。なお、上記パーフルオロアルキルエーテル構造は、これらの繰り返し単位の１種単独で構成されていてもよいし、２種以上の組み合わせであってもよい。 Examples of the repeating unit —C a F 2a O— represented by the above formula (5) include the following units. In addition, the said perfluoroalkyl ether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
−ＣＦ2Ｏ−
−ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ−
−Ｃ（ＣＦ3）2Ｏ−
これらの中では、特に下記単位が好適である。
−ＣＦ2Ｏ−
−ＣＦ2ＣＦ2Ｏ−
−ＣＦ2ＣＦ2ＣＦ2Ｏ−
−ＣＦ（ＣＦ3）ＣＦ2Ｏ−
-CF 2 O-
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3 ) CF 2 O-
-CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-
-C (CF 3) 2 O-
Of these, the following units are particularly preferred.
-CF 2 O-
-CF 2 CF 2 O-
-CF 2 CF 2 CF 2 O-
-CF (CF 3 ) CF 2 O-
この（Ａ）成分の直鎖状パーフルオロポリエーテル化合物におけるアルケニル基としては、炭素数２〜８、特に炭素数２〜６で、かつ末端にＣＨ2＝ＣＨ−構造を有するものが好ましく、例えば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等の末端にＣＨ2＝ＣＨ−構造を有する基、特にビニル基、アリル基等が好ましい。このアルケニル基は、直鎖状パーフルオロポリエーテル化合物の主鎖の両端部に直接結合していてもよいし、二価の連結基、例えば、−ＣＨ2−、−ＣＨ2Ｏ−又は−Ｙ−ＮＲ−ＣＯ−［但し、Ｙは−ＣＨ2−又は As the alkenyl group in the linear perfluoropolyether compound of the component (A), those having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms and having a CH 2 ═CH— structure at the terminal are preferable. , Vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups and the like, groups having a CH 2 ═CH— structure, particularly vinyl groups, allyl groups and the like are preferable. This alkenyl group may be directly bonded to both ends of the main chain of the linear perfluoropolyether compound, or may be a divalent linking group such as —CH 2 —, —CH 2 O— or —Y. —NR—CO—, wherein Y is —CH 2 — or
であり、Ｒは水素原子、メチル基、フェニル基又はアリル基である。］等を介して結合していてもよい。アルケニル基は１分子中に少なくとも２個有する。
And R is a hydrogen atom, a methyl group, a phenyl group or an allyl group. ] Or the like. There are at least two alkenyl groups in one molecule.
（Ａ）成分としては、下記一般式（６）又は（７）で表されるポリフルオロジアルケニル化合物を挙げることができる。
ＣＨ2＝ＣＨ−（Ｘ）p−Ｒｆ2−（Ｘ’）p−ＣＨ＝ＣＨ2 （６）
ＣＨ2＝ＣＨ−（Ｘ）p−Ｑ−Ｒｆ2−Ｑ−（Ｘ’）p−ＣＨ＝ＣＨ2 （７）
［式中、Ｘは独立に−ＣＨ2−、−ＣＨ2Ｏ−、−ＣＨ2ＯＣＨ2−又は−Ｙ−ＮＲ1−ＣＯ−（但し、Ｙは−ＣＨ2−又は下記構造式（Ｚ）で示される基であり、Ｒ1は水素原子、メチル基、フェニル基又はアリル基である。）であり、Ｘ’は−ＣＨ2−、−ＯＣＨ2−、−ＣＨ2ＯＣＨ2−又は−ＣＯ−ＮＲ2−Ｙ’−（但し、Ｙ’は−ＣＨ2−又は下記構造式（Ｚ’）で示される基であり、Ｒ2は水素原子、メチル基、フェニル基又はアリル基である。）である。
Examples of the component (A) include polyfluorodialkenyl compounds represented by the following general formula (6) or (7).
CH 2 = CH- (X) p -Rf 2 - (X ') p -CH = CH 2 (6)
CH 2 = CH- (X) p -Q-Rf 2 -Q- (X ') p -CH = CH 2 (7)
[-CH 2 wherein, X is independently -, - CH 2 O -, -
Ｒｆ2は二価のパーフルオロポリエーテル構造であり、上記式（５）、即ち（ＣaＦ2aＯ）qで示されるものが好ましい。Ｑは炭素数１〜１５の二価の炭化水素基であり、エーテル結合を含んでいてもよく、具体的にはアルキレン基、エーテル結合を含んでいてもよいアルキレン基である。ｐは独立に０又は１である。］
Rf 2 is a divalent perfluoropolyether structure, and is preferably represented by the above formula (5), that is, (C a F 2a O) q . Q is a C1-C15 divalent hydrocarbon group which may contain an ether bond, specifically an alkylene group or an alkylene group which may contain an ether bond. p is independently 0 or 1. ]
このような（Ａ）成分の直鎖状パーフルオロポリエーテル化合物としては、特に下記一般式（１）で示されるものが好適である。 As such a linear perfluoropolyether compound (A), those represented by the following general formula (1) are particularly suitable.
上記式（１）の直鎖状パーフルオロポリエーテル化合物は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリエチレン換算重量平均分子量が１０，０００〜１００，０００、特に１０，０００〜５０，０００であることが望ましい。分子量が１０，０００未満の場合は、ガソリンや各種溶剤に対する膨潤が大きくなる。特に、ガソリン対する膨潤が６％以上となり、耐ガソリン性が要求される部材としては特性を満足することができない。また、分子量が１００，０００を超える場合は、粘度が高く、作業性に劣るため実用性がない。 The linear perfluoropolyether compound of the above formula (1) has a weight average molecular weight in terms of polyethylene by gel permeation chromatography (GPC) of 10,000 to 100,000, particularly 10,000 to 50,000. Is desirable. When the molecular weight is less than 10,000, swelling with gasoline and various solvents increases. In particular, the swelling with respect to gasoline becomes 6% or more, and the characteristics cannot be satisfied as a member requiring gasoline resistance. Moreover, when molecular weight exceeds 100,000, since viscosity is high and it is inferior to workability | operativity, there is no practicality.
一般式（１）で表される直鎖状パーフルオロポリエーテル化合物の具体例としては、下記式で表されるものが挙げられる。 Specific examples of the linear perfluoropolyether compound represented by the general formula (1) include those represented by the following formula.
更に、本発明では、上記式（１）の直鎖状パーフルオロポリエーテル化合物を目的に応じた所望の重量平均分子量に調節するため、予め上記したような直鎖状パーフルオロポリエーテル化合物を分子内にＳｉＨ基を２個含有する有機ケイ素化合物と通常の方法及び条件でヒドロシリル化反応させ、鎖長延長した生成物を（Ａ）成分として使用することも可能である。 Furthermore, in the present invention, in order to adjust the linear perfluoropolyether compound of the above formula (1) to a desired weight average molecular weight according to the purpose, the linear perfluoropolyether compound as described above is used as a molecule. It is also possible to use, as component (A), a product obtained by subjecting an organosilicon compound containing two SiH groups therein to a hydrosilylation reaction by a conventional method and conditions to extend the chain length.
［（Ｂ）成分］
（Ｂ）成分は、（Ａ）成分の架橋剤、鎖長延長剤として作用するものである。この（Ｂ）成分は、１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物である。但し、（Ａ）成分又は後述する（Ｅ），（Ｆ）成分との相溶性、分散性、硬化後の均一性等の観点から、１分子中に１個以上の一価のパーフルオロアルキル基、一価のパーフルオロオキシアルキル基、二価のパーフルオロアルキレン基又は二価のパーフルオロオキシアルキレン基を有しているものを使用することができる。
[Component (B)]
The component (B) acts as a crosslinking agent and a chain extender for the component (A). This component (B) is an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule. However, one or more monovalent perfluoroalkyl groups in one molecule from the viewpoint of compatibility with component (A) or components (E) and (F) described later, dispersibility, uniformity after curing, and the like. A monovalent perfluorooxyalkyl group, a divalent perfluoroalkylene group, or a divalent perfluorooxyalkylene group can be used.
かかる（Ｂ）成分としては、特許第２９９０６４６号公報及び特開２０００−２４８１６６号公報記載の公知の有機ケイ素化合物が挙げられるが、特に限定されるものではない。 Examples of the component (B) include known organosilicon compounds described in Japanese Patent No. 2990646 and Japanese Patent Application Laid-Open No. 2000-248166, but are not particularly limited.
このような有機ケイ素化合物としては、特に下記一般式（８）で示されるものが有用である。 As such an organosilicon compound, those represented by the following general formula (8) are particularly useful.
Ｒｆ3の一価のパーフルオロアルキル基又はパーフルオロポリエーテル基としては、下記一般式で示される基を例示することができる。
一価のパーフルオロアルキル基：
ＣbＦ2b+1−
（但し、ｂは１〜２０、好ましくは２〜１０の整数である。）
Examples of the monovalent perfluoroalkyl group or perfluoropolyether group of Rf 3 include groups represented by the following general formula.
Monovalent perfluoroalkyl group:
C b F 2b + 1 −
(However, b is an integer of 1-20, preferably 2-10.)
一価のパーフルオロオキシアルキル基： Monovalent perfluorooxyalkyl group:
Ｒ3は炭素数１〜２０、特に炭素数１〜１２の一価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基等のアルキル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、ヘキセニル基等のアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基等のアリール基、ベンジル基、フェニルエチル基、フェニルプロピル基等のアラルキル基などが挙げられるが、好ましくは脂肪族不飽和結合を有さないものが好ましい。 R 3 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and pentyl. Groups, hexyl groups, octyl groups, decyl groups and other alkyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, etc. Examples thereof include aryl groups such as alkenyl group, phenyl group, tolyl group, xylyl group and naphthyl group, and aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group, but preferably have no aliphatic unsaturated bond. Those are preferred.
また、Ｒ4は炭素数２〜２０の二価炭化水素基であり、エーテル結合、アミド結合、カルボニル結合、又はエステル結合を含んでもよい二価の連結基である。かかる連結基としては、アルキレン基、アリーレン基やこれらの組み合わせでも、あるいはこれらにエーテル結合酸素原子（−Ｏ−）、アミド結合（−ＮＲＣＯ−）、カルボニル結合（−ＣＯ−）、エステル結合（−ＣＯＯ−）の１種又は２種以上を介在するものであってもよく、炭素数２〜１２のものが好ましく、下記の基等が挙げられる。なお、−ＮＲＣＯ−基におけるＲは水素原子、炭素数１〜４のアルキル基、又はフェニル基である。
−ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2ＯＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2−ＮＨ−ＣＯ−
−ＣＨ2ＣＨ2ＣＨ2−Ｎ（Ｐｈ）−ＣＯ−
（但し、Ｐｈはフェニル基である。）
−ＣＨ2ＣＨ2ＣＨ2−Ｎ（ＣＨ3）−ＣＯ−
−ＣＨ2ＣＨ2ＣＨ2−Ｏ−ＣＯ−
R 4 is a divalent hydrocarbon group having 2 to 20 carbon atoms, and is a divalent linking group that may include an ether bond, an amide bond, a carbonyl bond, or an ester bond. Examples of such a linking group include an alkylene group, an arylene group, a combination thereof, or an ether bond oxygen atom (—O—), an amide bond (—NRCO—), a carbonyl bond (—CO—), an ester bond (— One or two or more of (COO-) may be interposed, and those having 2 to 12 carbon atoms are preferred, and the following groups are exemplified. Note that R in the —NRCO— group is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.
—CH 2 CH 2 —
—CH 2 CH 2 CH 2 —
-CH 2 CH 2 CH 2 OCH 2 -
—CH 2 CH 2 CH 2 —NH—CO—
-CH 2 CH 2 CH 2 -N ( Ph) -CO-
(However, Ph is a phenyl group.)
-CH 2 CH 2 CH 2 -N ( CH 3) -CO-
—CH 2 CH 2 CH 2 —O—CO—
上記（Ｂ）成分の配合量は、（Ａ）成分及び後述の（Ｅ）成分を硬化する有効量であり、特に本組成物中の上記（Ａ）成分及び（Ｅ）成分が有するアルケニル基の合計の１モルに対し、（Ｂ）成分のヒドロシリル基（Ｓｉ−Ｈ）が好ましくは０．２〜２モル、より好ましくは０．５〜１．５モルとなる量である。ヒドロシリル基（Ｓｉ−Ｈ）が少なすぎると、架橋度合が不十分となる結果、硬化物が得られない場合があり、また、多すぎると硬化時に発泡してしまう場合がある。 The blending amount of the component (B) is an effective amount for curing the component (A) and the later-described component (E), and particularly the alkenyl group of the component (A) and the component (E) in the composition. The amount of the hydrosilyl group (Si-H) of the component (B) is preferably 0.2 to 2 mol, more preferably 0.5 to 1.5 mol, with respect to 1 mol in total. If the amount of hydrosilyl groups (Si—H) is too small, the degree of crosslinking may be insufficient, and as a result, a cured product may not be obtained, and if too large, foaming may occur during curing.
［（Ｃ）成分］ [Component (C)]
本発明の（Ｃ）成分である、酸性ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体は、一般に金属粉、ハイドロタルサイト構造を有する粉体化合物等の酸性ガス及び／又は硫黄含有ガスを化学的に吸着しうるもの、又は細孔構造を有する粉体活性炭等の酸性ガス及び／又は硫黄含有ガスを物理的に吸着しうるものが挙げられる。 The inorganic powder capable of chemically and / or physically adsorbing the acid gas and / or sulfur-containing gas, which is the component (C) of the present invention, is generally a metal powder, a powder compound having a hydrotalcite structure, or the like. Examples include those capable of chemically adsorbing acid gas and / or sulfur-containing gas, and those capable of physically adsorbing acid gas and / or sulfur-containing gas such as powdered activated carbon having a pore structure.
ここで、酸性ガス、硫黄含有ガスとは、一般的に腐食性ガスとして知られているもので、具体的にはＮＯｘ、ＳＯｘ、酢酸、蟻酸、硝酸、硫酸、硫黄、亜硫酸等のガスが挙げられる。 Here, the acid gas and the sulfur-containing gas are generally known as corrosive gases, and specifically include gases such as NOx, SOx, acetic acid, formic acid, nitric acid, sulfuric acid, sulfur, and sulfurous acid. It is done.
（Ｃ）成分としての金属粉は、酸性ガス及び／又は硫黄含有ガスを化学的に酸化あるいは硫化することにより、酸性ガス及び／又は硫黄含有ガスの電気電子部品への到達を防止もしくは遅延することを可能とするものである。その効果があるものとして、銀、銅、鉄、ニッケル、アルミニウム、錫、亜鉛などが例示される。この中でも金属粉の安定性、価格的な面から、銅粉が好ましい。
また、その形状・性質は、効果を得るためには制限はないが、組成物に与える不純物・流動性などの点から、アトマイズ粉が好ましい。
かかる金属粉としては、銅粉末（鱗片状）３Ｌ３（福田金属箔工業株式会社製商品名）、銅粉末（アトマイズ粉）ＦＣＣ−ＳＰ−９９（福田金属箔工業株式会社製商品名）、鉄粉末（アトマイズ粉）アトメル３００Ｍ（株式会社神戸製鋼所製商品名）等が挙げられる。
The metal powder as component (C) prevents or delays the acid gas and / or sulfur-containing gas from reaching the electric / electronic component by chemically oxidizing or sulfurating the acid gas and / or sulfur-containing gas. Is possible. Silver, copper, iron, nickel, aluminum, tin, zinc etc. are illustrated as what has the effect. Among these, copper powder is preferable from the viewpoint of stability and price of metal powder.
Further, the shape and properties are not limited in order to obtain the effect, but atomized powder is preferable from the viewpoint of impurities and fluidity imparted to the composition.
As such metal powder, copper powder (scale-like) 3L3 (trade name, manufactured by Fukuda Metal Foil Industry Co., Ltd.), copper powder (atomized powder) FCC-SP-99 (trade name, manufactured by Fukuda Metal Foil Industry Co., Ltd.), iron powder (Atomized powder) Atmel 300M (trade name, manufactured by Kobe Steel, Ltd.) and the like.
ハイドロタルサイト構造を有する粉体化合物は、マグネシウムとアルミニウムの化合物であり、酸性ガス及び／又は硫黄含有ガスのアニオンとの交換性を有しており、酸性ガス及び／又は硫黄含有ガスの電気電子部品への到達を防止もしくは遅延することを可能とするものである。 The powder compound having a hydrotalcite structure is a compound of magnesium and aluminum, and has an exchange property with an anion of an acid gas and / or a sulfur-containing gas. This makes it possible to prevent or delay the arrival of parts.
ハイドロタルサイトは、従来公知のものを使用することができる。具体的には、特許第２５０１８２０号公報、特許第２５１９２７７号公報、特許第２７１２８９８号公報、特許第３１６７８５３号公報、特公平０６−０５１８２６号公報、特開平０９−１１８８１０号公報、特開平１０−１５８３６０号公報、特開平１１−２４０９３７号公報、特開平１１−３１０７６６号公報、特開２０００−１５９５２０号公報、特開２０００−２３０１１０号公報、特開２００２−０８０５６６号公報等で、半導体封止材料のイオントラップ材として耐湿信頼性、耐熱特性向上のために数多くの使用例が挙げられており、これらに記載されているものであればいずれでもよい。 A conventionally well-known thing can be used for a hydrotalcite. Specifically, Japanese Patent No. 2501820, Japanese Patent No. 2519277, Japanese Patent No. 2712898, Japanese Patent No. 3167853, Japanese Patent Publication No. 06-051826, Japanese Patent Laid-Open No. 09-118810, Japanese Patent Laid-Open No. 10-158360. No. 11-240937, No. 11-310766, No. 2000-159520, No. 2000-230110, No. 2002-080566, etc. Numerous use examples are given for improving the moisture resistance reliability and the heat resistance characteristics of the ion trap material, and any of those described in these examples may be used.
特に、下記一般式（９）で表される化合物が挙げられる。
ＭｇxＡｌy（ＯＨ）2x+3y+2z（ＣＯ3）z・αＨ2Ｏ （９）
（ｘ，ｙ，ｚ はそれぞれ０＜ｙ／ｘ≦１、０≦ｚ／ｙ＜１．５なる関係を有し、αは整数を示す。）
In particular, the compound represented by the following general formula (9) is exemplified.
Mg x Al y (OH) 2x + 3y + 2z (CO 3) z · αH 2 O (9)
(X, y, z have a relationship of 0 <y / x ≦ 1, 0 ≦ z / y <1.5, respectively, and α represents an integer.)
かかるハイドロタルサイト構造を有する粉体化合物としては、具体的には
１．２５Ｍｇ（ＯＨ）2・Ａｌ（ＯＨ）3・ｚＣＯ3・αＨ2Ｏ
Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏ
Ｍｇ4.5Ａｌ2（ＯＨ）13ＣＯ3・３．５Ｈ2Ｏ
等が例示される。
Specifically, the powder compound having such a hydrotalcite structure is 1.25 Mg (OH) 2 · Al (OH) 3 · zCO 3 · αH 2 O.
Mg 6 Al 2 (OH) 16 CO 3 / 4H 2 O
Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O
Etc. are exemplified.
ハイドロタルサイトはアニオン交換性を有しており、例えばＨＣｌガスに対しては下記反応式により示す化学吸着が行われる。
Ｍｇ6Ａｌ2（ＯＨ）16ＣＯ3・４Ｈ2Ｏ ＋ ２ＨＣｌ
→ Ｍｇ6Ａｌ2（ＯＨ）13Ｃｌ2・ｎＨ2Ｏ ＋ Ｈ2Ｏ ＋ ＣＯ2
Hydrotalcite has anion exchange properties, and for example, chemical adsorption represented by the following reaction formula is performed on HCl gas.
Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O + 2HCl
→ Mg 6 Al 2 (OH) 13 Cl 2 .nH 2 O + H 2 O + CO 2
かかるハイドロタルサイト構造を有する粉体化合物としては、キョーワード５００、キョーワード１０００、ＤＨＴ−４Ａ−２（いずれも協和化学工業株式会社製商品名）等が挙げられる。 Examples of the powder compound having such a hydrotalcite structure include KYOWARD 500, KYOWARD 1000, DHT-4A-2 (all trade names manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.
また、本発明の（Ｃ）成分である、酸性ガス及び／又は硫黄含有ガスを物理的に吸着し得る無機粉体は、細孔構造を有する粉体活性炭であり、その細孔構造中に酸性ガス及び／又は硫黄含有ガスに対し選択的吸着性を有しており、酸性ガス及び／又は硫黄含有ガスの電気電子部品への到達を防止もしくは遅延することを可能とするものである。粉体活性炭としては、木質系原料をベースに賦活法により生産した水蒸気炭、薬品賦活法により精製した塩化亜鉛炭等が例示される。 In addition, the inorganic powder capable of physically adsorbing the acid gas and / or sulfur-containing gas, which is the component (C) of the present invention, is a powdered activated carbon having a pore structure, and the pore structure is acidic. It has a selective adsorptivity with respect to gas and / or sulfur-containing gas, and makes it possible to prevent or delay the arrival of acid gas and / or sulfur-containing gas to electric and electronic parts. Examples of the powdered activated carbon include steam coal produced by an activation method based on a wood-based raw material, zinc chloride coal purified by a chemical activation method, and the like.
かかる細孔構造を有する粉体活性炭としては、活性炭白鷺Ａ、白鷺Ｃ、白鷺Ｍ、白鷺Ｐ（いずれも日本エンバイロケミカルズ株式会社製商品名）等が挙げられる。 Examples of the powdered activated carbon having such a pore structure include activated carbon Hakuho A, Hakuho C, Hakuho M, and Hakuho P (all trade names manufactured by Nippon Enviro Chemicals Co., Ltd.).
上記無機粉体の添加量は、酸性ガス及び／又は硫黄含有ガスの電気電子部品への到達を防止もしくは遅延する効果が得られる量が必要であり、その目的を達成するために、（Ａ）成分又は（Ａ），（Ｅ）成分の合計１００質量部に対し０．１〜５０質量部が添加される。組成物の流動性や、硬化物の体積抵抗率を維持するため、０．３〜３０質量部、より好ましくは０．５〜２０質量部である。 The amount of the inorganic powder added is required to be an amount capable of preventing or delaying the arrival of the acid gas and / or the sulfur-containing gas to the electric and electronic parts. In order to achieve the object, (A) 0.1-50 mass parts is added with respect to a total of 100 mass parts of a component or (A) and (E) component. In order to maintain the fluidity of the composition and the volume resistivity of the cured product, the content is 0.3 to 30 parts by mass, more preferably 0.5 to 20 parts by mass.
また、パーフルオロポリエーテル硬化物が導電性（体積抵抗率：１×１０9Ω・ｃｍ未満）となると、電気電子部品としては不満足となるため、体積抵抗率を維持できるようにする必要があり、粉体の種類及び配合量を、パーフルオロポリエーテル硬化物の体積抵抗率が１×１０9Ω・ｃｍ以上、特に１×１０10Ω・ｃｍ以上となるように選定することが必要である。 Moreover, when the perfluoropolyether cured product becomes conductive (volume resistivity: less than 1 × 10 9 Ω · cm), it becomes unsatisfactory as an electric / electronic component, so it is necessary to maintain the volume resistivity. It is necessary to select the type and amount of the powder so that the volume resistivity of the cured perfluoropolyether is 1 × 10 9 Ω · cm or more, particularly 1 × 10 10 Ω · cm or more. .
［（Ｄ）成分］
本発明の（Ｄ）成分のヒドロシリル化反応触媒は、（Ａ）成分及び（Ｅ）成分中のアルケニル基と、（Ｂ）成分中のヒドロシリル基との付加反応を促進する触媒である。このヒドロシリル化反応触媒は、一般に貴金属の化合物であり、高価格であることから、比較的入手しやすい白金又は白金化合物がよく用いられる。
[(D) component]
The hydrosilylation reaction catalyst of the component (D) of the present invention is a catalyst that promotes the addition reaction between the alkenyl group in the components (A) and (E) and the hydrosilyl group in the component (B). Since this hydrosilylation reaction catalyst is generally a noble metal compound and is expensive, platinum or platinum compounds that are relatively easily available are often used.
白金化合物としては、例えば塩化白金酸又は塩化白金酸とエチレン等のオレフィンとの錯体、アルコールやビニルシロキサンとの錯体、シリカ、アルミナ、カーボン等を担持した金属白金等を挙げることができる。白金化合物以外の白金族金属触媒として、ロジウム、ルテニウム、イリジウム、パラジウム系化合物も知られており、例えばＲｈＣｌ（ＰＰｈ3）3、ＲｈＣｌ（ＣＯ）（ＰＰｈ3）2、Ｒｕ3（ＣＯ）12、ＩｒＣｌ（ＣＯ）（ＰＰｈ3）2、Ｐｄ（ＰＰｈ3）4等を例示することができる。 Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinyl siloxane, metal platinum carrying silica, alumina, carbon or the like. Rhodium, ruthenium, iridium and palladium compounds are also known as platinum group metal catalysts other than platinum compounds. For example, RhCl (PPh 3 ) 3 , RhCl (CO) (PPh 3 ) 2 , Ru 3 (CO) 12 , IrCl (CO) (PPh 3 ) 2 , Pd (PPh 3 ) 4 and the like can be exemplified.
ヒドロシリル化反応触媒の配合量は、触媒量とすることができるが、通常（Ａ）、（Ｂ）及び（Ｅ）成分の合計量１００質量部に対して０．１〜１００ｐｐｍ（白金換算）の割合で配合することが好ましい。 The compounding amount of the hydrosilylation reaction catalyst can be a catalytic amount, but is usually 0.1 to 100 ppm (in terms of platinum) with respect to 100 parts by mass of the total amount of the components (A), (B) and (E). It is preferable to mix | blend in a ratio.
［（Ｅ）成分］
（Ｅ）成分は、１分子中に１個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する、ポリフルオロモノアルケニル化合物である。特に、下記式（２）のポリフルオロモノアルケニル化合物が好ましい。
Ｒｆ1−（Ｘ’）p−ＣＨ＝ＣＨ2 （２）
［式中、Ｘ’及びｐは上記と同じであり、Ｒｆ1は、下記一般式で示される。
Ｆ−［ＣＦ（ＣＦ3）ＣＦ2Ｏ］w−ＣＦ（ＣＦ3）−
（式中、ｗは１〜５００、好ましくは２〜２００の整数で表される。）］
[(E) component]
Component (E) is a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain. In particular, a polyfluoromonoalkenyl compound of the following formula (2) is preferable.
Rf 1 − (X ′) p —CH═CH 2 (2)
[Wherein, X ′ and p are the same as described above, and Rf 1 is represented by the following general formula.
F- [CF (CF 3 ) CF 2 O] w -CF (CF 3 )-
(W is represented by an integer of 1 to 500, preferably 2 to 200.)]
上記一般式（２）で表されるポリフルオロモノアルケニル化合物の具体例としては、例えば、下記のものが挙げられる。 Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (2) include the following.
上記式（２）のポリフルオロモノアルケニル化合物の配合量は、硬化性パーフルオロポリエーテルゲル組成物において、本組成物中の上記（Ａ）成分の直鎖状パーフルオロポリエーテルジアルケニル化合物とこの（Ｅ）成分とが、（Ａ）成分２５〜６５質量部、（Ｅ）成分７５〜３５質量部の割合で、（Ａ）成分と（Ｅ）成分の合計量が１００質量部となるように選定される。 The compounding amount of the polyfluoromonoalkenyl compound of the above formula (2) is such that in the curable perfluoropolyether gel composition, the linear perfluoropolyether dialkenyl compound as the component (A) in the composition and this (E) Component is the ratio of (A) component 25-65 mass parts, (E) component 75-35 mass parts, and the total amount of (A) component and (E) component will be 100 mass parts. Selected.
［（Ｆ）成分］
本発明のパーフルオロポリエーテル系ゴム及びゲル組成物は、（Ｆ）成分として−ＣaＦ2aＯ−の繰り返し（ａは上記したと同様）単位を含むパーフルオロポリエーテル構造を有する、アルケニル基を含有しない無官能フッ素ポリマーを更に含有することができる。この無官能フッ素ポリマーは、特に直鎖状のものが好ましい。
[(F) component]
The perfluoropolyether rubber and gel composition of the present invention has an alkenyl group having a perfluoropolyether structure containing a repeating unit of -C a F 2a O- (a is the same as described above) as the component (F). It is possible to further contain a non-functional fluoropolymer that does not contain. This non-functional fluoropolymer is particularly preferably a linear one.
（Ｆ）成分である直鎖状パーフルオロポリエーテル化合物は、該成分を配合することにより、物性等を損なうことなく、耐薬品性、耐溶剤性、低温特性に優れた組成物を与える。特に、パーフルオロポリエーテル系ゴム組成物及びゲル組成物に配合した場合には、ガラス転移温度を下げるなど低温特性に優れた特性を付与することができる。 The linear perfluoropolyether compound as component (F) provides a composition excellent in chemical resistance, solvent resistance, and low-temperature characteristics by blending the component without impairing physical properties and the like. In particular, when blended with a perfluoropolyether rubber composition and a gel composition, characteristics excellent in low temperature characteristics such as lowering the glass transition temperature can be imparted.
（Ｆ）成分としては、下記一般式（３）、（４）で表される化合物からなる群から選ばれる直鎖状パーフルオロポリエーテル化合物が好ましく用いられる。
Ａ−Ｏ−（ＣＦ2ＣＦ2ＣＦ2Ｏ）d−Ａ （３）
（式中、Ａは式：ＣeＦ2e+1−（ｅは１〜３）で表される基であり、ｄは１〜５００、好ましくは２〜２００の整数。）
Ａ−Ｏ−（ＣＦ2Ｏ）f（ＣＦ2ＣＦ2Ｏ）h−Ａ （４）
（式中、Ａは上記と同じであり、ｆ及びｈはそれぞれ１〜３００、好ましくは１〜１００の整数。）
As the component (F), a linear perfluoropolyether compound selected from the group consisting of compounds represented by the following general formulas (3) and (4) is preferably used.
A-O- (CF 2 CF 2 CF 2 O) d -A (3)
(In the formula, A is a group represented by the formula: C e F 2e + 1- (e is 1 to 3), and d is an integer of 1 to 500, preferably 2 to 200.)
A-O- (CF 2 O) f (
(In the formula, A is the same as above, and f and h are each an integer of 1 to 300, preferably 1 to 100.)
（Ｆ）成分の具体例としては、例えば、下記のものが挙げられる。
ＣＦ3Ｏ−（ＣＦ2ＣＦ2ＣＦ2Ｏ）n′−ＣＦ2ＣＦ3
ＣＦ3−［（ＯＣＦ2ＣＦ2）n′（ＯＣＦ2）m′］−Ｏ−ＣＦ3
（ｍ′＋ｎ′＝１〜２００、ｍ′＝１〜２００、ｎ′＝１〜２００）
Specific examples of the component (F) include the following.
CF 3 O- (CF 2 CF 2 CF 2 O) n '-
CF 3 - [(OCF 2 CF 2) n '(OCF 2) m'] -O-
(M ′ + n ′ = 1 to 200, m ′ = 1 to 200, n ′ = 1 to 200)
（Ｆ）成分の配合量は、パーフルオロポリエーテル系ゴム及びゲル組成物において異なるが、パーフルオロポリエーテル系ゲル組成物においては、前記（Ａ）成分及び（Ｅ）成分（ポリフルオロジアルケニル化合物とポリフルオロモノアルケニル化合物の合計量）１００質量部に対して２０〜１００質量部の割合であることが好ましい。また、パーフルオロポリエーテル系ゴム組成物においては、前記（Ａ）成分１００質量部に対して１０〜５０質量部の割合であることが好ましい。（Ｆ）成分は、１種単独でも２種以上を併用してもよい。 The blending amount of the component (F) differs in the perfluoropolyether rubber and the gel composition, but in the perfluoropolyether gel composition, the component (A) and the component (E) (polyfluorodialkenyl compound) And the total amount of the polyfluoromonoalkenyl compound) is preferably 20 to 100 parts by mass with respect to 100 parts by mass. Moreover, in a perfluoropolyether type rubber composition, it is preferable that it is a ratio of 10-50 mass parts with respect to 100 mass parts of said (A) component. As the component (F), one type may be used alone, or two or more types may be used in combination.
［その他の成分］
本組成物においては、上記の（Ａ）〜（Ｆ）成分以外にも、各種配合剤を添加することは任意である。ヒドロシリル化反応触媒の制御剤として、例えば１−エチニル−１−ヒドロキシシクロヘキサン、３−メチル−１−ブチン−３−オール、３，５−ジメチル−１−ヘキシン−３−オール、３−メチル−１−ペンテン−３−オール、フェニルブチノールなどのアセチレンアルコールや、３−メチル−３−ペンテン−１−イン、３，５−ジメチル−３−ヘキセン−１−イン等、あるいはポリメチルビニルシロキサン環式化合物、有機リン化合物等が挙げられ、その添加により硬化反応性と保存安定性を適度に保つことができる。
[Other ingredients]
In the present composition, it is optional to add various compounding agents in addition to the components (A) to (F). Examples of the control agent for the hydrosilylation reaction catalyst include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 3-methyl-1. -Acetylene alcohol such as penten-3-ol and phenylbutynol, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, etc., or polymethylvinylsiloxane cyclic A compound, an organic phosphorus compound, etc. are mentioned, The hardening reactivity and storage stability can be kept moderate by the addition.
無機質充填剤として、例えば煙霧質シリカ、溶融シリカ、結晶性シリカ、酸化鉄、酸化亜鉛、酸化チタン、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、カーボンブラック等が挙げられ、その添加により本組成物から得られる硬化物の硬さ・機械的強度を調整することができる。中空無機質充填剤又はゴム質の球状充填剤も添加できる。 Examples of the inorganic filler include fumed silica, fused silica, crystalline silica, iron oxide, zinc oxide, titanium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, and carbon black. The hardness and mechanical strength of the cured product can be adjusted. Hollow inorganic fillers or rubbery spherical fillers can also be added.
また、接着性を付与するためにエポキシ基、アルコキシ基等を含有する、公知の接着性付与剤を添加することもできる。これらの配合成分の使用量は、得られる組成物の特性及び硬化物の物性を損なわない限りにおいて任意である。 Moreover, in order to provide adhesiveness, the well-known adhesiveness imparting agent containing an epoxy group, an alkoxy group, etc. can also be added. The amount of these blending components used is arbitrary as long as the properties of the resulting composition and the physical properties of the cured product are not impaired.
［硬化物］
本発明のパーフルオロポリエーテルゴム及びゲル組成物は、上記した組成物を硬化させることにより、耐熱性、耐薬品性、耐溶剤性、撥水性、撥油性、耐候性等に優れている上、特に酸性ガス及び硫黄含有ガスの低透過性に優れる硬化物を形成させることができ、各種の用途に使用することができる。
[Cured product]
The perfluoropolyether rubber and gel composition of the present invention are excellent in heat resistance, chemical resistance, solvent resistance, water repellency, oil repellency, weather resistance and the like by curing the above-described composition. In particular, a cured product excellent in low permeability of acid gas and sulfur-containing gas can be formed, and can be used for various applications.
パーフルオロポリエーテルゴム硬化物は、（Ａ）成分１００質量部に対して、（Ｂ）成分を（Ａ）成分が有するアルケニル基の合計のモル数１に対して（Ｂ）成分のヒドロシリル基が０．２〜２．０モルとなる量、（Ｃ）成分が０．１〜５０質量部、（Ｄ）成分が（Ａ）、（Ｂ）成分の合計量に対して白金換算で０．１〜１００ｐｐｍを硬化させることにより形成させることができる。更には、ガラス転移温度低下の目的で（Ｆ）成分を１０〜５０質量部を添加することは任意である。 The cured product of perfluoropolyether rubber has 100 parts by mass of component (A), and (B) component has a hydrosilyl group of component (B) with respect to the total number of moles of alkenyl groups of component (A). The amount of 0.2 to 2.0 mol, 0.1 to 50 parts by mass of component (C), 0.1 to component (D), 0.1 in terms of platinum with respect to the total amount of components (A) and (B). It can be formed by curing ~ 100 ppm. Furthermore, it is optional to add 10 to 50 parts by mass of component (F) for the purpose of lowering the glass transition temperature.
ゴム硬化物の形成は、適当な型内に上記した組成物を注入して硬化を行う、組成物を適当な基板上にコーティングした後に硬化を行う、あるいは貼り合わせ等により従来公知の方法により行われる。硬化は、通常６０〜１５０℃の温度で３０〜１８０分程度の加熱処理によって容易に行うことができる。 The cured rubber is formed by injecting the above-described composition into a suitable mold and curing, coating the composition on a suitable substrate, curing, or bonding by a conventionally known method. Is called. Curing can be easily performed by a heat treatment for about 30 to 180 minutes, usually at a temperature of 60 to 150 ° C.
このようにして得られたゴム硬化物は、ＪＩＳ Ｋ６２４９による硬さが１０〜８０であり、ガラス転移温度が−５０℃以下のゴム材料である。 The rubber cured product thus obtained is a rubber material having a hardness according to JIS K6249 of 10 to 80 and a glass transition temperature of −50 ° C. or lower.
また、硬化性パーフルオロポリエーテルゲル硬化物は、（Ａ）成分２５〜６５質量部に対して、（Ｅ）成分が７５〜３５質量部で、（Ａ），（Ｅ）成分の合計が１００質量部であり、（Ｂ）成分が（Ａ）成分及び（Ｅ）成分が有するアルケニル基の合計のモル数１に対して（Ｂ）成分のヒドロシリル基が０．２〜２．０モルとなる量、（Ｃ）成分が０．１〜５０質量部、（Ｄ）成分が（Ａ），（Ｂ），（Ｅ）成分の合計量に対して白金換算で０．１〜１００ｐｐｍを硬化させることにより形成させることができる。更には、ガラス転移温度低下の目的で（Ｆ）成分を２０〜１００質量部添加することは任意である。 Moreover, curable perfluoropolyether gel hardened | cured material is 75-35 mass parts of (E) component with respect to 25-65 mass parts of (A) component, and the sum total of (A) and (E) component is 100. The hydrosilyl group of the component (B) is 0.2 to 2.0 mol relative to the total number of moles 1 of the alkenyl groups of the component (B) and the component (E). The amount of (C) component is 0.1 to 50 parts by mass, and the component (D) is 0.1 to 100 ppm in terms of platinum with respect to the total amount of components (A), (B), and (E). Can be formed. Furthermore, it is optional to add 20 to 100 parts by mass of component (F) for the purpose of lowering the glass transition temperature.
ゲル硬化物の形成は、適当な型内に上記した組成物を注入して硬化を行う、組成物を適当な基板上にコーティングした後に硬化を行う、あるいは貼り合わせ等により従来公知の方法により行われる。硬化は、通常６０〜１５０℃の温度で３０〜１８０分程度の加熱処理によって容易に行うことができる。 The gel-cured product is formed by injecting the above-described composition into a suitable mold and curing it, coating the composition on a suitable substrate and curing it, or pasting it by a conventionally known method. Is called. Curing can be easily performed by a heat treatment for about 30 to 180 minutes, usually at a temperature of 60 to 150 ° C.
このようにして得られたゲル硬化物は、ＪＩＳ Ｋ２２２０（又はＡＳＴＭ Ｄ−１４０３）稠度試験法（１／４コーン使用）で規定される針入度が１０〜１５０であり、ガラス転移温度が−５０℃以下のゲル材料である。 The gel cured product thus obtained has a penetration of 10 to 150 as defined by JIS K2220 (or ASTM D-1403) consistency test method (using 1/4 cone), and has a glass transition temperature of − It is a gel material of 50 ° C. or lower.
本発明のゴム及びゲル硬化物を用いたゴム及びゲル製品は、自動車用、化学プラント用、インクジェットプリンタ用、半導体製造ライン用、分析・理化学機器用、医療機器用、航空機用、燃料電池用等部材として、使用することができる。 Rubber and gel products using the rubber and gel cured product of the present invention are for automobiles, chemical plants, inkjet printers, semiconductor production lines, analytical / physical equipment, medical equipment, aircraft, fuel cells, etc. It can be used as a member.
更に詳述すると、本発明の組成物の硬化物を含むゴム及びゲル製品は、自動車用ゴム部品、化学プラント用ゴム部品、インクジェットプリンタ用ゴム部品、半導体用製造ライン用ゴム部品、分析・理化学機器用ゴム部品、医療機器用ゴム部品、航空機用ゴム部品、その他、テント膜材料、シーラント、成形部品、押出部品、被覆材、複写機ロール材料、電気電子用防湿コーティング材、センサー用ポッティング剤、燃料電池用シール材、積層ゴム布等を挙げることができる。 More specifically, rubber and gel products containing the cured product of the composition of the present invention include automotive rubber parts, rubber parts for chemical plants, rubber parts for inkjet printers, rubber parts for semiconductor production lines, analytical / physical equipment. Rubber parts for medical equipment, rubber parts for medical equipment, rubber parts for aircraft, others, tent film materials, sealants, molded parts, extruded parts, coating materials, copier roll materials, moisture-proof coating materials for electric and electronic equipment, potting agents for sensors, fuel Examples thereof include battery sealing materials and laminated rubber cloths.
自動車用ゴム部品としては、フューエル・レギュレータ用ダイヤフラム、パルセーションダンパ用ダイヤフラム、オイルプレッシャースイッチ用ダイヤフラム、ＥＧＲ用ダイヤフラム等のダイヤフラム類、キャニスタ用バルブ、パワーコントロール用バルブ等のバルブ類、クイックコネクター用のＯ−リング、インクジェッタ用Ｏ−リング等のＯ−リング類、オイルシール、シリンダヘッド用ガスケット等のシール材等が挙げられる。 Rubber parts for automobiles include diaphragms for fuel and regulators, diaphragms for pulsation dampers, diaphragms for oil pressure switches, diaphragms for EGR, valves for canisters, valves for power control, etc. Examples thereof include O-rings such as O-rings and O-rings for ink jetters, and sealing materials such as oil seals and cylinder head gaskets.
化学プラント用ゴム部品としては、ポンプ用ダイヤフラム、バルブ類、Ｏ−リング類、パッキン類、オイルシール、ガスケット等が挙げられる。 Examples of rubber parts for chemical plants include pump diaphragms, valves, O-rings, packings, oil seals, gaskets, and the like.
インクジェットプリンタ用ゴム部品、半導体用製造ライン用ゴム部品としては、ダイヤフラム、弁、Ｏ−リング、パッキン、ガスケット等が挙げられる。 Examples of rubber parts for inkjet printers and semiconductor parts for semiconductor production lines include diaphragms, valves, O-rings, packings, and gaskets.
分析・理化学機器用ゴム部品、医療機器用ゴム部品としては、ポンプ用ダイヤフラム、Ｏ−リング、パッキン、バルブ、ジョント等が挙げられる。 Examples of rubber parts for analytical / physical and chemical equipment and rubber parts for medical equipment include diaphragms for pumps, O-rings, packings, valves, and Jonto.
航空機用ゴム部品としては、航空機用エンジンオイル、ジェット燃料、ハイドローリックオイル、スカイドロール等の流体配管用Ｏ−リング、フェースシール、パッキン、ガスケット、ダイヤフラム、バルブ等が挙げられる。燃料電池用ゴム部品としては電極間のシール材をはじめとして水素、空気及び冷却水配管のＯ−リング、フェースシール、パッキン、ガスケット、ダイヤフラム、バルブ等が挙げられる。 Examples of aircraft rubber parts include O-rings for fluid piping such as aircraft engine oil, jet fuel, hydraulic oil, and skid roll, face seals, packings, gaskets, diaphragms, valves, and the like. Examples of the fuel cell rubber parts include a seal material between electrodes, an O-ring of hydrogen, air and cooling water piping, a face seal, packing, a gasket, a diaphragm, a valve, and the like.
電気電子用防湿コーティング材、センサー用ポッティング剤としては、ガス圧センサー、液圧センサー、温度センサー、湿度センサー、回転センサー、Ｇセンサー、タイミングセンサー、エアフローメーター、電子回路、半導体モジュール、各種コントロールユニット等が挙げられる。 Moisture-proof coating materials for electrical and electronic use and potting agents for sensors include gas pressure sensors, hydraulic pressure sensors, temperature sensors, humidity sensors, rotation sensors, G sensors, timing sensors, air flow meters, electronic circuits, semiconductor modules, various control units, etc. Is mentioned.
圧力を検出してその検出値に応じたレベルの電気信号を発生する検出部を、耐薬品性を有する保護部材で被覆して保護するようにした圧力センサーに、保護部材として本発明の硬化性パーフルオロポリエーテルゴム組成物及び／又は硬化性パーフルオロポリエーテルゲル組成物を用いることができる。特に、従来の圧力センサーにおける、自動車のインテークマニホールドの吸気圧センサーのようにガソリン等の薬品に曝される環境で使用される場合のみならず、自動車の排気圧センサーやオートマチックトランスミッションセンサー等におけるＮＯｘ、ＳＯｘ等の酸性ガスに曝される環境でも耐酸性、耐薬品性を向上させることができる。 The pressure sensor which detects the pressure and generates an electric signal at a level corresponding to the detected value is covered with a protective member having chemical resistance to protect the pressure sensor, and the curable property of the present invention as the protective member. A perfluoropolyether rubber composition and / or a curable perfluoropolyether gel composition can be used. In particular, the conventional pressure sensor is used not only in an environment exposed to chemicals such as gasoline, such as an intake pressure sensor of an intake manifold of an automobile, but also NOx in an exhaust pressure sensor or an automatic transmission sensor of an automobile, Acid resistance and chemical resistance can be improved even in an environment exposed to an acid gas such as SOx.
また、本発明の組成物の硬化物をポッティング、コーティング等する場合、基材との密着性あるいは接着性を向上させるために公知のプライマーを併用することが有用である。プライマーにより、基材界面からの薬品及び溶剤の浸入を防止することができ、部品全体の耐酸性、耐薬品性及び耐溶剤性を向上することができる。 In addition, when potting or coating the cured product of the composition of the present invention, it is useful to use a known primer in combination in order to improve adhesion or adhesion to the substrate. The primer can prevent entry of chemicals and solvents from the substrate interface, and can improve the acid resistance, chemical resistance, and solvent resistance of the entire component.
プライマーとしては、シランカップリング剤を主体とするシラン系プライマー、オルガノハイドロジェンポリシロキサンを主体とするプライマー、合成ゴムを主成分とするプライマーや、アクリル樹脂を主成分とするプライマー、ウレタン樹脂を主成分とするプライマー、エポキシ樹脂を主成分とするプライマー、また本発明のパーフルオロポリエーテルゴム組成物に接着付与剤を添加した組成物もプライマーとして使用できる。 Primers mainly include silane-based primers mainly composed of silane coupling agents, primers mainly composed of organohydrogenpolysiloxanes, primers mainly composed of synthetic rubber, primers mainly composed of acrylic resins, and urethane resins. A primer comprising an ingredient, an epoxy resin as a main component, and a composition obtained by adding an adhesion-imparting agent to the perfluoropolyether rubber composition of the present invention can also be used as a primer.
以下、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例で％は質量％を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% indicates mass%.
［実施例１〜６、比較例１〜５］
下記原料を使用し、表１に示すパーフルオロポリエーテルゴム及びパーフルオロポリエーテルゲル組成物を調製した。
このゴム及びゲル組成物を１５０℃、１時間の硬化条件にて硬化し、その硬さ、体積抵抗率を測定すると共に、下記方法によって腐食試験を行った。結果を表１に併記する。
[Examples 1-6, Comparative Examples 1-5]
Using the following raw materials, perfluoropolyether rubber and perfluoropolyether gel composition shown in Table 1 were prepared.
This rubber and gel composition was cured under curing conditions of 150 ° C. for 1 hour, its hardness and volume resistivity were measured, and a corrosion test was conducted by the following method. The results are also shown in Table 1.
原料
（ａ）無機粉末
（ａ−１）金粉末（鱗片状）（ＳＡ０５：石福金属興業株式会社製商品名）
（ａ−２）銅粉末（鱗片状）（３Ｌ３：福田金属箔工業株式会社製商品名）
（ａ−３）銅粉末（アトマイズ粉）（ＦＣＣ−ＳＰ−９９：福田金属箔工業株式会社製商品名）
（ａ−４）鉄粉末（アトマイズ粉）（アトメル３００Ｍ：株式会社神戸製鋼所製商品名）
（ａ−５）活性炭（白鷺Ａ：日本エンバイロケミカルズ株式会社製商品名）
（ａ−６）合成ハイドロタルサイト（キョーワード５００：協和化学工業株式会社製商品名）
（ａ−７）合成ハイドロタルサイト（キョーワード１０００：協和化学工業株式会社製商品名）
（ａ−８）シリカ 煙霧性シリカ（Ａｅｒｏｓｉｌ Ｒ−９７２：日本アエロジル社製商品名）
Raw material (a) Inorganic powder (a-1) Gold powder (scale-like) (SA05: Product name manufactured by Ishifuku Metal Industry Co., Ltd.)
(A-2) Copper powder (scale-like) (3L3: trade name, manufactured by Fukuda Metal Foil Industry Co., Ltd.)
(A-3) Copper powder (atomized powder) (FCC-SP-99: Fukuda Metal Foil Industry Co., Ltd. trade name)
(A-4) Iron powder (atomized powder) (Atmel 300M: trade name manufactured by Kobe Steel)
(A-5) Activated carbon (Shirakaba A: Nippon Enviro Chemicals Co., Ltd. trade name)
(A-6) Synthetic hydrotalcite (KYOWARD 500: trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)
(A-7) Synthetic hydrotalcite (KYOWARD 1000: trade name, manufactured by Kyowa Chemical Industry Co., Ltd.)
(A-8) Silica fumed silica (Aerosil R-972: product name manufactured by Nippon Aerosil Co., Ltd.)
（ｂ）パーフルオロポリエーテルオイル
（ｂ−１）
(B) Perfluoropolyether oil (b-1)
（ｃ）ハイドロシロキサン
（ｃ−１）
(C) Hydrosiloxane (c-1)
（ｄ）白金−ジビニルテトラメチルジシロキサン錯体／トルエン溶液（白金含有量０．５％）
（ｅ）硬化制御剤 エチニルシクロヘキサノール／５０％トルエン溶液
（ｆ）ＦＥ５７（信越化学工業株式会社製商品名）：トリフルオロプロピル基含有シリコーンをベースとしたフルオロシリコーンゲル
（ｇ）ＫＥ１０５２（信越化学工業株式会社製商品名）：ジメチルシリコーンをベースとしたシリコーンゲル
(D) Platinum-divinyltetramethyldisiloxane complex / toluene solution (platinum content 0.5%)
(E) Curing controller Etynylcyclohexanol / 50% toluene solution (f) FE57 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.): Fluorosilicone gel based on trifluoropropyl group-containing silicone (g) KE1052 (Shin-Etsu Chemical Co., Ltd.) Product name): Silicone gel based on dimethyl silicone
腐食性試験Ａ
図１に示したように、ガラス瓶１中に銀メッキを施した銅板２を入れ、その上にジメチルシリコーンゲル３を硬化させ、更にその上に上記パーフルオロポリエーテル組成物４を３ｍｍの厚さに硬化させる。更にその上にポリエチレン製の容器５の中に０．１０ｇの硫黄粉６を乗せ、金属キャップ７で密封した。
これを８０℃の恒温器に放置し、２８日後の銀メッキの腐食程度を目視で観察した。
○：腐食無し
×：腐食有り（黒色化）
Corrosion test A
As shown in FIG. 1, a silver-plated
This was left in an incubator at 80 ° C., and the degree of corrosion of the silver plating after 28 days was visually observed.
○: No corrosion ×: Corrosion present (blackening)
腐食性試験Ｂ
図１に示したように、ガラス瓶１中に銀メッキを施した銅板２を入れ、その上にジメチルシリコーンゲル３を硬化させ、更にその上に上記パーフルオロポリエーテル組成物４を３ｍｍの厚さに硬化させる。更にその上にポリエチレン製の容器５の中に０．３０ｇの３６％塩酸水溶液６を乗せ、金属キャップ７で密封した。
これを８０℃の恒温器に放置し、２８日後の銀メッキの腐食程度を目視で観察した。
○：腐食無し
×：腐食有り（黒色化）
Corrosion test B
As shown in FIG. 1, a silver-plated
This was left in an incubator at 80 ° C., and the degree of corrosion of the silver plating after 28 days was visually observed.
○: No corrosion ×: Corrosion present (blackening)
１ ガラス瓶
２ 銀メッキ銅板
３ シリコーンゲル
４ パーフルオロポリエーテル硬化物
５ ポリエチレン容器
６ 硫黄又は塩酸
７ キャップ
1
Claims (13)
（Ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物 硬化有効量
（Ｃ）酸性ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体
０．１〜５０質量部
（Ｄ）ヒドロシリル化反応触媒 触媒量
を含有し、硬化してゴムを形成することを特徴とする硬化性パーフルオロポリエーテル組成物。 (A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure containing a repeating unit of -C a F 2a O- in the main chain (A is an integer of 1 to 6) 100 parts by mass (B) Organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule Curing effective amount (C) Acid gas and / or sulfur-containing gas Inorganic powder that can be adsorbed physically and / or physically
0.1 to 50 parts by mass (D) Hydrosilylation reaction catalyst A curable perfluoropolyether composition containing a catalytic amount and cured to form a rubber.
（Ｅ）１分子中に１個のアルケニル基を有し、かつ主鎖中にパーフルオロポリエーテル構造を有する、ポリフルオロモノアルケニル化合物 ７５〜３５質量部
（但し、（Ａ），（Ｅ）成分の合計量を１００質量部とする）
（Ｂ）１分子中にケイ素原子に結合した水素原子を少なくとも２個有する有機ケイ素化合物 硬化有効量
（Ｃ）酸性ガス及び／又は硫黄含有ガスを化学的及び／又は物理的に吸着し得る無機粉体
０．１〜５０質量部
（Ｄ）ヒドロシリル化反応触媒 触媒量
を含有し、硬化してゲルを形成することを特徴とする硬化性パーフルオロポリエーテル組成物。 (A) A linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure containing a repeating unit of -C a F 2a O- in the main chain (A is an integer of 1 to 6) 25 to 65 parts by mass (E) Polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain 75 to 35 parts by mass
(However, the total amount of components (A) and (E) is 100 parts by mass)
(B) Organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule Curing effective amount (C) Inorganic powder capable of chemically and / or physically adsorbing acid gas and / or sulfur-containing gas body
0.1 to 50 parts by mass (D) Hydrosilylation reaction catalyst A curable perfluoropolyether composition containing a catalytic amount and cured to form a gel.
Ｒｆ1−（Ｘ’）p−ＣＨ＝ＣＨ2 （２）
［式中、Ｘ’は−ＣＨ2−、−ＯＣＨ2−、−ＣＨ2ＯＣＨ2−又は−ＣＯ−ＮＲ2−Ｙ−（但し、Ｙは−ＣＨ2−又は下記構造式（Ｚ’）で示される基であり、
Ｒ2は水素原子、メチル基、フェニル基又はアリル基である。）であり、ｐは０又は１である。Ｒｆ1は、下記一般式
Ｆ−［ＣＦ（ＣＦ3）ＣＦ2Ｏ］w−ＣＦ（ＣＦ3）−
（式中、ｗは１〜５００の整数で表される。）で示されるパーフルオロポリエーテル構造である。］
で表されるポリフルオロモノアルケニル化合物である請求項２記載のパーフルオロポリエーテル組成物。 (E) component is the following general formula (2)
Rf 1 − (X ′) p —CH═CH 2 (2)
[Wherein, X ′ represents —CH 2 —, —OCH 2 —, —CH 2 OCH 2 — or —CO—NR 2 —Y— (where Y represents —CH 2 — or the following structural formula (Z ′). The group shown,
R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group. And p is 0 or 1. Rf 1 is represented by the following formula F- [CF (CF 3) CF 2 O] w -CF (CF 3) -
(Wherein w is represented by an integer of 1 to 500). ]
The perfluoropolyether composition according to claim 2, which is a polyfluoromonoalkenyl compound represented by the formula:
で表される直鎖状パーフルオロポリエーテル化合物である請求項１乃至７のいずれか１項に記載の硬化性パーフルオロポリエーテル組成物。 The component (A) is represented by the following general formula (1)
The curable perfluoropolyether composition according to claim 1, which is a linear perfluoropolyether compound represented by the formula:
Ａ−Ｏ−（ＣＦ2ＣＦ2ＣＦ2Ｏ）d−Ａ （３）
［式中、Ａは式：ＣeＦ2e+1−（ｅは１〜３）で表される基であり、ｄは１〜５００の整数。］、及び、下記一般式（４）
Ａ−Ｏ−（ＣＦ2Ｏ）f（ＣＦ2ＣＦ2Ｏ）h−Ａ （４）
（式中、Ａは上記と同じであり、ｆ及びｈはそれぞれ１〜３００の整数。）
で表される化合物からなる群から選ばれる少なくとも１種の直鎖状ポリフルオロ化合物を含有することを特徴とする請求項１乃至８のいずれか１項に記載のパーフルオロポリエーテル組成物。 The perfluoropolyether composition may further contain the following general formula (3) as component (F):
A-O- (CF 2 CF 2 CF 2 O) d -A (3)
[Wherein, A is a group represented by the formula: C e F 2e + 1- (e is 1 to 3), and d is an integer of 1 to 500. And the following general formula (4)
A-O- (CF 2 O) f (CF 2 CF 2 O) h -A (4)
(In the formula, A is the same as above, and f and h are each an integer of 1 to 300.)
The perfluoropolyether composition according to any one of claims 1 to 8, comprising at least one linear polyfluoro compound selected from the group consisting of compounds represented by:
11. A pressure sensor that detects and protects a detection unit that generates an electric signal at a level corresponding to the detected value with a protective member having chemical resistance, and is protected as a protective member. A pressure sensor for automobiles using the curable perfluoropolyether composition according to any one of the above.
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| JP2005002142A (en) * | 2003-06-09 | 2005-01-06 | Shin Etsu Chem Co Ltd | Adhesive composition and its manufacturing method |
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| JP4855643B2 (en) * | 2003-09-25 | 2012-01-18 | ダイソー株式会社 | Rubber composition for vulcanization excellent in acid resistance and vulcanized rubber material thereof |
| JP4582287B2 (en) * | 2003-10-27 | 2010-11-17 | 信越化学工業株式会社 | Low contamination adhesive composition |
| US20050277731A1 (en) * | 2004-06-11 | 2005-12-15 | Shin-Etsu Chemical Co., Ltd. | Curable perfluoropolyether compositions and rubber or gel articles comprising the same |
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2006
- 2006-02-07 JP JP2006029683A patent/JP4784743B2/en active Active
- 2006-02-10 US US11/350,767 patent/US7671160B2/en not_active Expired - Fee Related
- 2006-02-14 EP EP06250785A patent/EP1693398B1/en active Active
- 2006-02-14 DE DE602006000776T patent/DE602006000776T2/en active Active
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- 2011-04-13 JP JP2011088996A patent/JP5664424B2/en active Active
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| JPH11172108A (en) * | 1997-12-12 | 1999-06-29 | Shin Etsu Chem Co Ltd | Electroconductive fluororesin composition |
| JP2003031028A (en) * | 2001-07-17 | 2003-01-31 | Shin Etsu Chem Co Ltd | Conductive composition |
| JP2004010808A (en) * | 2002-06-10 | 2004-01-15 | Shin Etsu Chem Co Ltd | Fluororubber composition and method for producing the same |
| JP2004043590A (en) * | 2002-07-10 | 2004-02-12 | Shin Etsu Chem Co Ltd | Curable composition and electrical and electronic parts |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2043147A2 (en) | 2007-09-28 | 2009-04-01 | Shin-Etsu Chemical Co., Ltd. | Automotive electric/electronic package |
| KR101838265B1 (en) | 2011-06-16 | 2018-03-13 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Room temperature curable fluoropolyether rubber composition and cured product thereof |
| JP2016056315A (en) * | 2014-09-11 | 2016-04-21 | 信越化学工業株式会社 | Fluorosilicone rubber composition and rubber component used around engine of transport |
| JP2020030168A (en) * | 2018-08-24 | 2020-02-27 | 公立大学法人大阪 | Temperature sensor |
| JP7188692B2 (en) | 2018-08-24 | 2022-12-13 | 公立大学法人大阪 | temperature sensor |
| JP2022110886A (en) * | 2021-01-19 | 2022-07-29 | 信越化学工業株式会社 | Method for producing addition-curable silicone composition |
| JP7475791B2 (en) | 2021-01-19 | 2024-04-30 | 信越化学工業株式会社 | Method for producing addition-curable silicone composition |
Also Published As
| Publication number | Publication date |
|---|---|
| US7671160B2 (en) | 2010-03-02 |
| JP4784743B2 (en) | 2011-10-05 |
| DE602006000776D1 (en) | 2008-05-08 |
| JP5664424B2 (en) | 2015-02-04 |
| DE602006000776T2 (en) | 2009-04-09 |
| JP2011137182A (en) | 2011-07-14 |
| EP1693398B1 (en) | 2008-03-26 |
| US20060183859A1 (en) | 2006-08-17 |
| EP1693398A1 (en) | 2006-08-23 |
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